Dispersant composition

ABSTRACT

The present invention relates to a composition containing a particulate solid, a non-polar organic medium, and a compound obtained/obtainable by reacting an aromatic amine with hydrocarbyl-substituted acylating agent, wherein the hydrocarbyl-substituted acylating agent is selected from the group consisting of an oligomer or polymer from condensation polymerization of a hydroxy-substituted C 10-30  carboxylic acid into a polyester, an optionally hydroxy-substituted C 10-30  carboxylic acid, a C 10-30 -hydrocarbyl substituted acylating agent, and a polyolefin-substituted maleic anhydride. The invention further provides compositions for inks, thermoplastics, plasticizers, plastisols, crude grinding and flush.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority from PCT Application Serial No.PCT/US2011/036,622 filed on May 16, 2011, which claims the benefit ofU.S. Provisional Application No. 61/346,556 filed on May 20, 2010.

FIELD OF INVENTION

The present invention relates to a composition containing a particulatesolid, a non-polar organic medium, and a compound obtained/obtainable byreacting an aromatic amine with hydrocarbyl-substituted acylating agent.The invention further provides compositions for coatings, inks, toners,plastic materials (such as thermoplastics), plasticisers, plastisols,crude grinding and flush.

BACKGROUND OF THE INVENTION

Many formulations such as inks, paints, mill-bases and plasticsmaterials require effective dispersants for uniformly distributing aparticulate solid in a non-polar organic medium.

Numerous publications disclose polyester amine dispersants derived froma poly(C₂₋₄-alkylene imine) such as polyethylene imine to which isattached a polyester chain. The polyester chain may be derived from12-hydroxy stearic acid, as disclosed in U.S. Pat. No. 4,224,212, or itmay be derived from two or more different hydroxy carboxylic acids. GB 1373 660 discloses polyester amine dispersants obtainable by reaction ofa polyester from hydroxycarboxylic acid with diamine, especiallyalkylene diamines and salts thereof.

SUMMARY OF THE INVENTION

One objective of the present invention is to provide compounds that arecapable of at least one of improving colour strength, increasing aparticulate solid load, forming improved dispersions, having improvedbrightness, and producing a composition with reduced viscosity.

In one embodiment, the invention provides a composition comprising aparticulate solid, a non-polar organic medium, and a compoundobtained/obtainable by reacting an aromatic amine with ahydrocarbyl-substituted acylating agent, wherein thehydrocarbyl-substituted acylating agent is selected from the groupconsisting of an oligomer or polymer from condensation polymerisation ofa hydroxy-substituted C₁₀₋₃₀ carboxylic acid into a polyester, anoptionally hydroxy-substituted C₁₀₋₃₀ carboxylic acid, aC₁₀₋₃₀-hydrocarbyl substituted acylating agent, and apolyolefin-substituted acylating agent (typically succinic anhydride).

The compound may have a number average molecular weight of 500 to20,000, or 600 to 15,000, or 700 to 5000.

The aromatic amine may be mono-functional when reacting with thehydrocarbyl-substituted acylating agent but typically di- orpoly-functional.

In one embodiment, the aromatic amine to hydrocarbyl-substitutedacylating agent mole ratio may be in the range of 2:1 to 1:10, or 2:1 to1:4, or 1:1 to 1:3, or 1:1 to 1:2, or 1:2.

The hydrocarbyl-substituted acylating agent may be at least 50 mol %, orat least 75 mol %, or at least 90 mol % mono-functional or di-functional(when in the form of an anhydride) when reacted with the aromatic amine.

The particulate solid may be a pigment or a filler.

The non-polar organic medium may, for instance, include a mineral oil,an aliphatic hydrocarbon, an aromatic hydrocarbon, a plastic material(typically a thermoplastic resin), or a plasticiser.

The present invention also provides a composition comprising aparticulate solid (typically a pigment or filler), a non-polar organicmedium and a compound of the invention described above.

In one embodiment, the invention provides a paint or ink comprising aparticulate solid, a non-polar organic medium, a film-forming resin anda compound of the invention disclosed herein.

The ink may be an ink-jet ink, a gravure ink, or an offset ink.

In one embodiment, the invention provides a composition comprising acompound of the present invention, a particulate solid (typically apigment or filler), and a non-polar organic medium, wherein the organicmedium may be a plastics material. The plastic material may be athermoplastic resin.

In one embodiment, the invention provides for the use of the compounddescribed herein as a dispersant in a composition disclosed herein.

In one embodiment, the invention provides a compound obtained/obtainableby reacting an aromatic amine with a hydrocarbyl-substituted acylatingagent, wherein the hydrocarbyl-substituted acylating agent is selectedfrom the group consisting of an oligomer or polymer from condensationpolymerisation of a hydroxy-substituted C₁₀₋₃₀ carboxylic acid into apolyester, and an optionally hydroxy-substituted C₁₀₋₃₀ carboxylic acid,or mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a composition and use disclosed hereinabove.

Aromatic Amine

The aromatic amine includes aniline, nitroaniline, aminocarbazole,4-aminodiphenylamine (ADPA), and coupling products of ADPA. In oneembodiment, the amine may be 4-aminodiphenylamine (ADPA), or couplingproducts of ADPA. In one embodiment, the amine may be coupling productsof ADPA. In one embodiment, the aromatic amine may not be a heterocycle.

Coupled products of ADPA may be represented by the formula (1):

wherein independently each variable,R¹ may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);R² may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);U may be an aliphatic, alicyclic or aromatic group, with the provisothat when U is aliphatic, the aliphatic group may be linear or branchedalkylene group containing 1 to 5, or 1 to 2 carbon atoms; andw may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).

In one embodiment, the coupled ADPA of Formula (1) may be represented byFormula (1a):

wherein independently each variable,R¹ may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);R² may be hydrogen or a C₁₋₅ alkyl group (typically hydrogen);U may be an aliphatic, alicyclic or aromatic group, with the provisothat when U is aliphatic, the aliphatic group may be linear or branchedalkylene group containing 1 to 5, or 1 to 2 carbon atoms; andw may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).

Alternatively, the compound of Formula (1a) may also be represented by:

wherein each variable U, R¹, and R² are the same as described above andw is 0 to 9 or 0 to 3 or 0 to 1 (typically 0).

Examples of an amine having at least 3 aromatic groups may berepresented by any of the following Formulae (2) and/or (3):

A person skilled in the art will appreciate that compounds of Formulae(2) and (3) may also react with the aldehyde described below to formacridine derivatives. Acridine derivatives that may be formed includecompounds represented by Formula (2a) or (3a) below. In addition tothese compounds representing these formulae, a person skilled in the artwill also appreciate that other acridine structures may be possiblewhere the aldehyde reacts with other benzyl groups bridged with the >NHgroup. Examples of acridine structures include those represented byFormulae (2a) and (3a):

Any or all of the N-bridged aromatic rings are capable of such furthercondensation and perhaps aromatisation. One other of many possiblestructures is shown in Formula (3b):

Examples of the coupled ADPA includebis[p-(p-aminoanilino)phenyl]-methane,2-(7-amino-acridin-2-ylmethyl)-N-4-{4-[4-(4-amino-phenylamino)-benzyl]-phenyl}-benzene-1,4-diamine,N⁴-{4-[4-(4-amino-phenylamino)-benzyl]-phenyl}-2-[4-(4-amino-phenylamino)-cyclohexa-1,5-dienylmethyl]-benzene-1,4-diamine,N-[4-(7-amino-acridin-2-ylmethyl)-phenyl]-benzene-1,4-diamine, ormixtures thereof.

The coupled ADPA may be prepared by a process comprising reacting thearomatic amine with an aldehyde. The aldehyde may be aliphatic,alicyclic or aromatic. The aliphatic aldehyde may be linear or branched.Examples of a suitable aromatic aldehyde include benzaldehyde oro-vanillin. Examples of an aliphatic aldehyde include formaldehyde (or areactive equivalent thereof such as formalin or paraformaldehyde),ethanal or propanal. Typically, the aldehyde may be formaldehyde orbenzaldehyde.

The acylating agent, from which the compound of the invention may bederivable, may have one or more acid functional groups, such as acarboxylic acid or anhydride thereof. Examples of an acylating agentinclude an alpha, beta-unsaturated mono- or polycarboxylic acid,anhydride ester or derivative thereof. Examples of an acylating agentinclude (meth)acrylic acid, methyl(meth)acrylate, maleic acid oranhydride, fumaric acid, itaconic acid or anhydride, or mixturesthereof. In one embodiment, the acylating agent, from which the compoundof the invention may be derivable may, be maleic anhydride, or mixturesthereof.

In one embodiment, the compound of the invention may beobtained/obtainable by reacting an aromatic amine with ahydroxy-substituted C₁₀₋₃₀ carboxylic acid, or mixtures thereof.

The hydroxy-substituted C₁₀₋₃₀ carboxylic acid may typically bepolymerised to form a polyester. The polyester may be a polymerisationproduct of a hydroxy-substituted carboxylic acid of general formulaHO—X—COOH, wherein X is a divalent saturated or unsaturated aliphaticradical containing at least 4 carbon atoms between the hydroxyl andcarboxylic acid groups. The hydroxy-substituted C₁₀₋₃₀ carboxylic acidmay also be in a mixture with a C₁₀₋₃₀ carboxylic acid that is free fromhydroxyl groups.

X may contain 12-20 carbon atoms; and that there are between 3 and 14,or 8 and 14 carbon atoms between the carboxylic acid and hydroxy groups.

Examples of the hydroxy-substituted C₁₀₋₃₀ carboxylic acid may includericinoleic acid, 12-hydroxystearic acid, a mixture of 9- and10-hydroxystearic acids, 10-hydroxyundecanoic acid, 12-hydroxydodecanoicacid, 4-hydroxydecanoic acid, 5-hydroxydecanoic acid (ordelta-decanolactone), or 5-hydroxydodecanoic acid (or deltadodecanolactone). In different embodiments, the hydroxy-substitutedC₁₀₋₃₀ carboxylic acid may be ricinoleic acid, 12-hydroxystearic acid,or a mixture of 9- and 10-hydroxystearic acids. In one embodiment, thehydroxy-substituted C₁₀₋₃₀ carboxylic acid may be a mixture ofricinoleic acid and either 12-hydroxystearic acid or 9- and10-hydroxystearic acids.

The polyester may have 4 to 20 repeat units of the hydroxy-substitutedC₁₀₋₃₀ carboxylic acid.

The polyester may be a homopolymer or a copolymer. The copolymer may beeither a random or block copolymer.

In one embodiment, the compound of the invention may beobtained/obtainable by reacting an aromatic amine with an optionallyhydroxy-substituted C₁₀₋₃₀ carboxylic acid (typically a C₁₀₋₃₀carboxylic acid), or mixtures thereof.

The optionally hydroxy-substituted C₁₀₋₃₀ carboxylic acid may includericinoleic acid, 12-hydroxystearic acid, capric acid, lauric acid,myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, ormixtures thereof. In one embodiment, the C₁₀₋₃₀ carboxylic acid mayinclude lauric acid or stearic acid. In one embodiment, the optionallyhydroxy-substituted C₁₀₋₃₀ carboxylic acid may include a mixture of (i)at least one of ricinoleic acid, or 12-hydroxystearic acid, and (ii) atleast one of C₁₀₋₃₀ carboxylic acid such as lauric acid or stearic acid.

In one embodiment, the compound of the invention may beobtained/obtainable by reacting one mole of an aromatic amine with a oneto two moles of a C₁₀₋₃₀ carboxylic acid, or mixtures thereof. Thecompound may be particularly useful in a composition including a plasticmaterial.

In one embodiment, the compound of the invention may beobtained/obtainable by reacting an aromatic amine with a mixture of (i)C₁₀₋₃₀-hydrocarbyl substituted acylating agent (as described above), and(ii) a hydroxy-substituted C₁₀₋₃₀ carboxylic acid (as described above).In one embodiment, the mixture includes (i) stearic acid, and (ii) apolyester of hydroxystearic acid or a polyester of ricinoleic acid.

In one embodiment, the compound of the invention may beobtained/obtainable by reacting an aromatic amine with aC₁₀₋₃₀-hydrocarbyl substituted acylating agent, or mixtures thereof.

The C₁₀₋₃₀-hydrocarbyl substituted acylating agent may be analk(en)yl-substituted succinic acid, anhydride, or partial estersthereof. Examples of suitable succinic anhydrides include dodecylsuccinic anhydride, hexadecyl succinic anhydride, octadecyl succinicanhydride, eicosyl succinic anhydride, C₂₄₋₂₈-alkyl succinic anhydride,dodecenyl succinic anhydride, hexadecenyl succinic anhydride,octadecenyl succinic anhydride, eicosenyl succinic anhydride,C₂₄₋₂₈-alkenyl succinic anhydride, or mixtures thereof. In oneembodiment, the C₁₀₋₃₀-hydrocarbyl substituted acylating agent may behexadecyl succinic anhydride, octadecyl succinic anhydride, or mixturesthereof.

In one embodiment, the compound of the invention may beobtained/obtainable by reacting an aromatic amine with apolyolefin-substituted succinic anhydride, or mixtures thereof.

The polyolefin-substituted succinic anhydride may be a polyisobutylenesuccinic anhydride. The polyisobutylene from which the polyisobutylenesuccinic anhydride is derivable may have a number average molecularweight of 300 to 5000, 450 to 4000, 500 to 3000 or 550 to 2500.Particular ranges of the number average molecular weight may include 550to 1000, or 750 to 1000, or 950 to 1000, or 1600 to about 2300.

The polyolefin may have a vinylidene group. The vinylidene group may bepresent on at least 2 wt. %, or at least 40%, or at least 50%, or atleast 60%, or at least 70% of the polyolefin molecules. Often, theamount of vinylidene group present is about 75%, about 80% or about 85%.

When the polyolefin is a polyisobutylene the polyolefin may be obtainedcommercially under the tradenames of Glissopal® 1000 or Glissopal® 2300(commercially available from BASF), TPC® 555, TPC® 575 or TPC® 595(commercially available from Texas Petrochemicals).

The polyolefin-substituted succinic anhydride may be obtained byreacting a polyolefin (typically polyisobutylene) with maleic anhydrideby Diels Alder or by an “ene” reaction. Both reactions are known in theart. In one embodiment, the polyolefin-substituted succinic anhydridemay be obtained by reacting a polyolefin (typically polyisobutylene)with maleic anhydride by an “ene” reaction.

The compound of the invention may be prepared by reacting an aromaticamine with a hydrocarbyl-substituted acylating agent at a reactiontemperature in the range of 80° C. to 220° C., or 100° C. to 200° C.

In one embodiment, the aromatic amine to hydrocarbyl-substitutedacylating agent mole ratio may be in the range of 2:1 to 1:10, or 2:1 to1:4, or 1:1 to 1:3, or 1:1 to 1:2, or 1:2. In one embodiment, thearomatic amine to hydrocarbyl-substituted acylating agent mole ratio maybe 1:1 to 1:2, or 1:2.

The reaction may be carried out in an inert atmosphere, for example,under nitrogen or argon, typically nitrogen.

The reaction may be a one-step process or a two-step process.

A two-step process may be employed if the hydrocarbyl-substitutedacylating agent is a polyester. The first step comprises forming apolyester by copolymerising a hydroxy-substituted C₁₀₋₃₀ carboxylic acidas described above. The reaction may also optionally be carried out inthe presence of a catalyst such as zirconium butoxide. Thepolymerisation step is known and is described for instance in U.S. Pat.No. 3,996,059. The second step comprises reacting the polyester with thearomatic amine.

Processes to prepare the compound of the invention when thehydrocarbyl-substituted acylating agent is a polyolefin-substitutedacylating agent is described in International Application U.S. Ser. No.09/065,452 (filed 23 Nov. 2009), also provisionally filed with U.S.Patent Application No. 61/118,012 (on 26 Nov. 2008). A process toprepare a compound of this type is shown below in EX1 and EX2.

Preparative Example 1 (EX1)

is a coupled aromatic amine head group synthesis. 500 mL of 2Mhydrochloric acid is added to a one-liter 4-neck flask equipped with anoverhead stirrer, thermowell, addition funnel with nitrogen line, andcondenser. 184.2 g of 4-aminodiphenylamine is added, and the flask isheated to 75° C. The addition funnel is then charged with 40.5 g of a37% formaldehyde solution and the solution is added drop-wise to theflask over a period of 30 minutes. The flask is maintained at 100° C.for 4 hours. The flask is then cooled to ambient temperature. 80 g of a50/50 wt./wt. solution of sodium hydroxide in water is added over 30minutes. At the end of the reaction, a solid product is obtained viafiltration. The resultant solid product is believed to primarily be thecompound of Formula (2) as described above. In addition, the resultantproduct may contain a small percentage of product based on Formula (3)as described above.

Preparative Example 2 (EX2)

is a reaction product of polyisobutylene succinic anhydride with theproduct of EX1. A three-liter, 4-neck flask equipped with an overheadstirrer, thermowell, subsurface inlet with nitrogen line, and Dean-Starktrap with condenser is charged with polyisobutylene succinic anhydride(1270.0 g) (where the polyisobutylene from which it is derived has anumber average molecular weight of 2000) and diluent oil (1400.1 g). Theflask is heated to 90° C. The product of EX1 (442.0 g) is added slowly.The temperature is then raised to 110° C. and held until the water fromreaction with the product of EX1 is removed. The temperature is thenraised to 160° C. and held for 10 hours. To the flask is added a portionof a diatomaceous earth filter aid, and then flask contents are filteredthrough a second portion of the diatomaceous earth filter aid. Theresultant product is a dark oil with a nitrogen content of 0.65 wt. %.

INDUSTRIAL APPLICATION

In one embodiment, the compound of the invention disclosed herein may bea dispersant, typically used for dispersing particulate solid materials.

The compound of the invention disclosed herein in different embodimentsmay be present in the composition of the invention in a range selectedfrom 0.1 to 50 wt. %, or 0.25 to 35 wt. %, and 0.5 to 30 wt. %.

The particulate solid present in the composition may be any inorganic ororganic solid material which is substantially insoluble in the non-polarorganic medium at the temperature concerned and which it is desired tostabilize in a finely divided form therein. The particulate solids maybe in the form of a granular material, a fibre, a platelet or in theform of a powder, often a blown powder. In one embodiment, theparticulate solid is a pigment of a filler. The pigment may be a organicor inorganic pigment, typically an organic pigment.

Examples of suitable particulate solids include pigments for solventinks; pigments, extenders, fillers, blowing agents and flame retardantsfor paints and plastics materials; dyes, especially disperse dyes;optical brightening agents and textile auxiliaries for solvent dyebaths,inks and other solvent application systems; solids for oil-based andinverse-emulsion drilling muds; metals; particulate ceramic materialsand magnetic materials for ceramics, piezoceramic printing, refactories,abrasives, foundry, capacitors, fuel cells, ferrofluids, conductiveinks, magnetic recording media, water treatment and hydrocarbon soilremediation; organic and inorganic nanodisperse solids, such as metal,metal oxides and carbon for electrodes in batteries; fibres such ascarbon and boron for composite materials; and biocides, agrochemicalsand pharmaceuticals which are applied as dispersions in organic media.

In one embodiment, the particulate solid may be an organic pigment fromany of the recognised classes of pigments described, for example, in theThird Edition of the Colour Index (1971) and subsequent revisions of,and supplements thereto, under the chapter headed “Pigments”. Examplesof organic pigments are those from the azo, disazo, trisazo, condensedazo, azo lakes, naphthol pigments, anthanthrone, anthrapyrimidine,anthraquinone, benzimidazolone, carbazole, diketopyrrolopyrrole,flavanthrone, indigoid pigments, indanthrone, isodibenzanthrone,isoindanthrone, isoindolinone, isoindoline, isoviolanthrone, metalcomplex pigments, oxazine, perylene, perinone, pyranthrone,pyrazoloquinazolone, quinacridone, quinophthalone, thioindigo,triarylcarbonium pigments, triphendioxazine, xanthene and phthalocyanineseries, especially copper phthalocyanine and its nuclear halogenatedderivatives, and also lakes of acid, basic and mordant dyes. Carbonblack, although strictly inorganic, behaves more like an organic pigmentin its dispersing properties. In one embodiment, the organic pigmentsare phthalocyanines, especially copper phthalocyanines, monoazos,disazos, indanthrones, anthranthrones, quinacridones,diketopyrrolopyrroles, perylenes and carbon black including single- andmulti-walled carbon nanotubes, reinforcing and non-reinforcing carbonblack, graphite, Buckminster fullerenes, asphaltene, and graphene.

In one embodiment, the solid particulate is not carbon black, or hasless than 80, 50, or 10 wt. % carbon and metal wear byproducts as acomponent of the particulate solid, based on the total weight of thesolid particulate.

Other useful particulate solids include flame retardants such aspentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenylether, hexabromocyclododecane, ammonium polyphosphate, melamine,melamine cyanurate, antimony oxide and borates; biocides or industrialmicrobial agents such as those mentioned in Tables 2, 3, 4, 5, 6, 7, 8and 9 of the chapter entitled “Industrial Microbial Agents” inKirk-Othmer's Encyclopedia of Chemical Technology, Volume 13, 1981,3^(rd) Edition, and agrochemicals such as the fungicides flutriafen,carbendazim, chlorothalonil and mancozeb.

The non-polar organic medium present in the composition of the inventionin one embodiment may be a plastics material and in another embodimentan organic liquid.

In one embodiment, non-polar organic liquids are compounds containingaliphatic groups, aromatic groups or mixtures thereof. The non-polarorganic liquids include non-halogenated aromatic hydrocarbons (e.g.,toluene and xylene), halogenated aromatic hydrocarbons (e.g.,chlorobenzene, dichlorobenzene, chlorotoluene), non-halogenatedaliphatic hydrocarbons (e.g., linear and branched aliphatic hydrocarbonscontaining six or more carbon atoms both fully and partially saturated),halogenated aliphatic hydrocarbons (e.g., dichloromethane, carbontetrachloride, chloroform, trichloroethane) and natural non-polarorganics (e.g., vegetable oil, sunflower oil, linseed oil, terpenes andglycerides).

In one embodiment, the non-polar organic medium includes at least 0.1%by weight, or 1% by weight or more of a polar organic liquid based onthe total organic liquid, with the proviso that the composition remainssubstantially non-polar. The non-polar medium may contain up to 5 wt. %or up to 10 wt. % of a polar organic liquid. Typically, the non-polarorganic medium is substantially free of, to free of a polar organicliquid. In one embodiment, the non-polar medium is substantially freeof, to free of water.

Examples of suitable polar organic liquids include amines, ethers,especially lower alkyl ethers, organic acids, esters, ketones, glycols,alcohols and amides. Numerous specific examples of such moderatelystrongly hydrogen bonding liquids are given in the book entitled“Compatibility and Solubility” by Ibert Mellan (published in 1968 byNoyes Development Corporation) in Table 2.14 on pages 39-40, and theseliquids all fall within the scope of the term polar organic liquid asused herein.

In one embodiment, polar organic liquids include dialkyl ketones, alkylesters of alkane carboxylic acids and alkanols, especially such liquidscontaining up to, and including, a total of 6 or 8 carbon atoms. Asexamples of the polar organic liquids include dialkyl and cycloalkylketones, such as acetone, methyl ethyl ketone, diethyl ketone,di-isopropyl ketone, methyl isobutyl ketone, di-isobutyl ketone, methylisoamyl ketone, methyl n-amyl ketone and cyclohexanone; alkyl esterssuch as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate,ethyl formate, methyl propionate, methoxy propylacetate and ethylbutyrate; glycols and glycol esters and ethers, such as ethylene glycol,2-ethoxyethanol, 3-methoxypropylpropanol, 3-ethoxypropylpropanol,2-butoxyethyl acetate, 3-methoxypropyl acetate, 3-ethoxypropyl acetateand 2-ethoxyethyl acetate; alkanols such as methanol, ethanol,n-propanol, isopropanol, n-butanol and isobutanol and dialkyl and cyclicethers such as diethyl ether and tetrahydrofuran. In one embodiment,solvents are alkanols, alkane carboxylic acids and esters of alkanecarboxylic acids.

Examples of organic liquids, which may be used as polar organic liquidsare film-forming resins. Examples of such film-forming resins includepolyamides, such as Versamid™ and Wolfamid™, and cellulose ethers, suchas ethyl cellulose and ethyl hydroxyethyl cellulose, nitrocellulose andcellulose acetate butyrate resins, including mixtures thereof. Examplesof resins include short oil alkyd/melamine-formaldehyde,polyester/melamine-formaldehyde, thermosettingacrylic/melamine-formaldehyde, long oil alkyd, polyether polyols andmulti-media resins, such as acrylic and urea/aldehyde.

The organic liquid may be a polyol, that is to say, an organic liquidwith two or more hydroxy groups. In one embodiment, polyols includealpha-omega diols or alpha-omega diol ethoxylates.

If desired, the compositions containing a non-polar organic medium maycontain other ingredients, for example, resins (where these do notalready constitute the organic medium), binders, co-solvents,cross-linking agents, fluidising agents, wetting agents,anti-sedimentation agents, plasticisers, surfactants, dispersants otherthan the compound of the present invention, humectants, anti-foamers,anti-cratering agents, rheology modifiers, heat stabilizers, lightstabilizers, UV absorbers, antioxidants, levelling agents, glossmodifiers, biocides and preservatives.

The plastics material may be a thermosetting resin or a thermoplasticresin. The thermosetting resins useful in this invention include resinswhich undergo a chemical reaction when heated, catalysed, or subject toultra-violet, laser light, infra-red, cationic, electron beam, ormicrowave radiation and become relatively infusible. Typical reactionsin thermosetting resins include oxidation of unsaturated double bonds,reactions involving epoxy/amine, epoxy/carbonyl, epoxy/hydroxyl,reaction of epoxy with a Lewis acid or Lewis base,polyisocyanate/hydroxy, amino resin/hydroxy moieties, free radicalreactions or polyacrylate, cationic polymerization of epoxy resins andvinyl ether and condensation of silanol. Examples of unsaturated resinsinclude polyester resins made by the reaction of one or more diacids oranhydrides with one or more diols. Such resins are commonly supplied asa mixture with a reactive monomer such as styrene or vinyltoluene andare often referred to as orthophthalic resins and isophthalic resins.Further examples include resins using dicyclopentadiene (DCPD) as aco-reactant in the polyester chain. Further examples also include thereaction products of bisphenol A diglycidyl ether with unsaturatedcarboxylic acids such as methacrylic acid, subsequently supplied as asolution in styrene, commonly referred to as vinyl ester resins.

Polymers with hydroxy functionality (frequently polyols) are widely usedin thermosetting systems to crosslink with amino resins orpolyisocyanates. The polyols include acrylic polyols, alkyd polyols,polyester polyols, polyether polyols and polyurethane polyols. Typicalamino resins include melamine formaldehyde resins, benzoguanamineformaldehyde resins, urea formaldehyde resins and glycolurilformaldehyde resins. Polyisocyanates are resins with two or moreisocyanate groups, including both monomeric aliphatic diisocyanates,monomeric aromatic diisocyanates and their polymers. Typical aliphaticdiisocyanates include hexamethylene diisocyanate, isophoronediisocyanate and hydrogenated diphenylmethane diisocyanate. Typicalaromatic isocyanates include toluene diisocyanates and biphenylmethanediisocyanates.

The plastics material such as a thermoset resin may be useful for partsin boat hulls, baths, shower trays, seats, conduits and bulkheads fortrains, trams, ships aircraft, body panels for automotive vehicles andtruck beds.

In one embodiment, thermoplastic resins include polyolefins, polyesters,polyamides, polycarbonates, polyurethanes, polystyrenics,poly(meth)acrylates, celluloses and cellulose derivatives. Saidcompositions may be prepared in a number of ways but melt mixing and drysolid blending are typical methods. Examples of a suitable thermoplasticinclude (low density, or linear low density or high density)polyethylene, polypropylene, polystyrene, polyethylene terephthalate(PET), polybutylene terephthalate (PBT), nylon 6, nylon 6/6, nylon 4/6,nylon 6/12, nylon and nylon 12, polymethylmethacrylate,polyethersulphone, polysulphones, polycarbonate, polyvinyl chloride(PVC), thermoplastic polyurethane, ethylene vinyl acetate (EVA), VictrexPEEK™ polymers (such asoxy-1,4-phenylenoeoxy-1,4-phenylene-carbonyl-1,4-phenylene polymers) andacrylonitrile butadiene styrene polymers (ABS); and various otherpolymeric blends or alloys.

If desired, the compositions containing plastic material may containother ingredients, for example, dispersants other than the compound ofthe present invention, antifogging agents, nucleators, blowing agents,flame retardants, process aids, surfactants, plasticisers, heatstabilizers, UV absorbers, anti-oxidants, fragrances, mould releaseaids, anti-static agents, anti-microbial agents, biocides, couplingagents, lubricants (external and internal), impact modifiers, slipagents, air release agents and viscosity depressants.

The compositions typically contain from 1 to 95% by weight of theparticulate solid, the precise quantity depending on the nature of thesolid and the quantity depending on the nature of the solid and therelative densities of the solid and the polar organic liquid. Forexample, a composition in which the solid is an organic material, suchas an organic pigment, in one embodiment contains from 15 to 60% byweight of the solid whereas a composition in which the solid is aninorganic material, such as an inorganic pigment, filler or extender, inone embodiment contains from 40 to 90% by weight of the solid based onthe total weight of composition.

The composition may be prepared by any of the conventional methods knownfor preparing dispersions. Thus, the solid, the organic medium and thedispersant may be mixed in any order, the mixture then being subjectedto a mechanical treatment to reduce the particles of the solid to anappropriate size, for example, by ball milling, bead milling, gravelmilling, high shear mixing or plastic milling until the dispersion isformed. Alternatively, the solid may be treated to reduce its particlesize independently or in admixture with either, the organic medium orthe dispersant, the other ingredient or ingredients then being added andthe mixture being agitated to provide the composition.

In one embodiment, the composition of the present invention is suited toliquid dispersions. In one embodiment, such dispersion compositionscomprise: (a) 0.5 to 40 parts of a particulate solid, (b) 0.5 to 30parts of a composition as disclosed herein above, and (c) 30 to 99 partsof an organic medium; wherein all parts are by weight and the amounts(a)+(b)+(c)=100.

In one embodiment, component a) includes 0.5 to 40 parts of a pigmentand such dispersions are useful as mill-bases, coatings, paints, toners,or inks.

If a composition is required including a particulate solid and acomposition as disclosed herein above in dry form, the organic liquid istypically volatile so that it may be readily removed from theparticulate solid by a simple separation means such as evaporation. Inone embodiment, the composition includes the organic liquid.

If the dry composition consists essentially of the composition asdisclosed herein above and the particulate solid, it typically containsat least 0.2%, at least 0.5% or at least 1.0% the composition asdisclosed herein above based on weight of the particulate solid. In oneembodiment, the dry composition contains not greater than 100%, notgreater than 50%, not greater than 20%, or not greater than 10% byweight of the composition as disclosed herein above based on the weightof the particulate solid. In one embodiment, the composition, asdisclosed herein above, is present at 0.6 wt. % to 8 wt. %.

As disclosed hereinbefore, the compositions of the invention aresuitable for preparing mill-bases wherein the particulate solid ismilled in an organic liquid in the presence of a composition, asdisclosed herein above, or salts thereof.

Thus, according to a still further embodiment of the invention, there isprovided a mill-base including a particulate solid, an organic liquidand a composition as disclosed herein above, or salts thereof.

Typically, the mill-base contains from 20 to 70% by weight particulatesolid based on the total weight of the mill-base. In one embodiment, theparticulate solid is not less than 10 or not less than 20% by weight ofthe mill-base. Such mill-bases may optionally contain a binder addedeither before or after milling. The binder is a polymeric materialcapable of binding the composition on volatilisation of the organicliquid.

Binders are polymeric materials including natural and syntheticmaterials. In one embodiment, binders include poly(meth)acrylates,polystyrenics, polyesters, polyurethanes, alkyds, polysaccharides suchas cellulose, and natural proteins such as casein. In one embodiment,the binder is present in the composition at more than 100% based on theamount of particulate solid, more than 200%, more than 300% or more than400%.

The amount of optional binder in the mill-base can vary over wide limitsbut is typically not less than 10%, and often not less than 20% byweight of the continuous/liquid phase of the mill-base. In oneembodiment, the amount of binder is not greater than 50% or not greaterthan 40% by weight of the continuous/liquid phase of the mill-base.

The amount of dispersant in the mill-base is dependent on the amount ofparticulate solid, but is typically from 0.5 to 5% by weight of themill-base. Continuous/liquid phase includes all of the liquid materials(e.g., solvent, liquid binder, dispersants, etc.) and any solid materialthat dissolves in the liquid materials after a short mixing period,e.g., it specifically excludes solid particulates that are dispersed inthe continuous liquid phase.

Dispersions and mill-bases made from the composition of the inventionare particularly suitable for use in aqueous, non-aqueous and solventfree formulations in which energy curable systems (ultra-violet, laserlight, infra-red, cationic, electron beam, microwave) are employed withmonomers, oligomers, etc., or a combination present in the formulation.They are particularly suitable for use in coatings such as paints,varnishes, inks, other coating materials and plastics. Suitable examplesinclude their use in low, medium and high solids paints, generalindustrial paints including baking, 2 component and metal coating paintssuch as coil and can coatings, powder coatings, UV-curable coatings,wood varnishes; inks, such as flexographic, gravure, offset,lithographic, letterpress or relief, screen printing and printing inksfor packaging printing, non impact inks such as ink jet inks, inks forink jet printers and print varnishes such as overprint varnishes; polyoland plastisol dispersions; non-aqueous ceramic processes, especiallytape-casting, gel-casting, doctor-blade, extrusion and injectionmoulding type processes, a further example would be in the preparationof dry ceramic powders for isostatic pressing; composites such as sheetmoulding and bulk moulding compounds, resin transfer moulding,pultrusion, hand-lay-up and spray-lay-up processes, matched diemoulding; construction materials like casting resins, cosmetics,personal care like nail coatings, sunscreens, adhesives, toners,plastics materials and electronic materials, such as coatingformulations for colour filter systems in displays including OLEDdevices, liquid crystal displays and electrophoretic displays, glasscoatings including optical fibre coatings, reflective coatings oranti-reflective coatings, conductive and magnetic inks and coatings.They are useful in the surface modification of pigments and fillers toimprove the dispersibility of dry powders used in the aboveapplications. Further examples of coating materials are given in BodoMuller, Ulrich Poth, Lackformulierung und Lackrezeptur, Lehrbuch frAusbildung und Praxis, Vincentz Verlag, Hanover (2003) and in P. G.Garrat, Strahlenhartung, Vincentz Verlag, Hanover (1996). Examples ofprinting ink formulations are given in E. W. Flick, Printing Ink andOverprint Varnish Formulations—Recent Developments, Noyes Publications,Park Ridge N.J., (1990) and subsequent editions.

In one embodiment, the composition of the invention further includes oneor more additional known dispersants.

The following examples provide illustrations of the invention. Theseexamples are non exhaustive and are not intended to limit the scope ofthe invention.

EXAMPLES

Inventive Compound 1 (IC1): 12-hydroxystearic acid (404.3 g) is placedpostionwise in a 1 L flask with heating until the acid melted. The flaskis attached to a Dean Stark apparatus with a stirrer. The mixture isthen heated to 110° C. under N₂ with stirring (at 230 rpm). The productof EX1 (as described above) (44.7 g) is then added portion wise througha powder funnel over 5 minutes. The reaction is then heated to 150° C.and held for 4 hours. 4.7 g of water is collected. The flask is cooledto 100° C. and the zirconium butoxide (80% solution) (2.6 g) is addedvia a pipette. A subsurface nitrogen sparge was added and set to 471.94cm³/min (or 1 scfh). The reaction is heated to 195° C. and held for 22hours. Water (8.3 g) is collected. The reaction is cooled and diluentoil is added (150.3 g). The resultant mixture is stirred for 1 hour. Afurther 147.2 g of diluent oil is added to homogenise for a further 30minutes at 100° C. The product is then filtered through Fax-5diatomaceous filter. A further 200 g of diluent oil is added tohomogenise for a further 30 minutes at 100° C. to give the finalproduct.

Inventive Compound 2 (IC2): 12-hydroxystearic acid (400.9 g) is placedpostionwise in a 1 L flask with heating until the acid melted. The flaskis attached to a Dean Stark apparatus with a stirrer. The mixture isthen heated to 110° C. under N₂ with stirring (at 240 rpm). 40.6 g of4-aminodiphenylamine is then added portion wise through a powder funnelover 5 minutes. The reaction is then heated to 150° C. and held for 4hours. The flask is cooled to 100° C. and the zirconium butoxide (80%solution) (2.5 g) is added via a pippette. A subsurface nitrogen spargewas added and set to 471.94 cm³/min (or 1 scfh). The reaction is heatedto 195° C. and held for 22 hours. The reaction is cooled to 100° C. anddiluent oil is added (133.5 g). The resultant mixture is stirred for 1hour at 100° C. The product is then filtered through Fax-5 diatomaceousfilter to give the final product.

Inventive Compound 3 (IC3): Ricinoleic acid (631.5 g) is placedpostionwise in a 1 L flask with heating until the acid melted. The flaskis attached to a Dean Stark apparatus with a stirrer. The mixture isthen heated to 110° C. under N₂ with stirring (at 200 rpm). 69.1 g ofthe product of EX1 described above is then added portion wise through apowder funnel over 10 minutes. The reaction is then heated to 150° C.and held for 4 hours. 14 g of water is collected. The flask is cooled to100° C. and the zirconium butoxide (80% solution) (4.0 g) is added via apippette. A subsurface nitrogen sparge was added and set to 471.94cm³/min (or 1 scfh). The reaction is heated to 195° C. and held for 19hours. Water (23.3 g) is collected. The reaction is cooled to 100° C.and diluent oil is added (220.3 g). The resultant mixture is stirred for1 hour at 100° C. The product is then filtered through Fax-5diatomaceous filter to give the final product.

Inventive Compound 4 (IC4): Ricinoleic acid (406 g; 1.362 moles) and theproduct of EX1 (89.6 g; 0.2357 moles) are charged to a 1 liter flask,under a nitrogen sparge. The flask is attached to a Dean Stark apparatuswith a stirrer. The flask is heated to 150° C. and maintained at thistemperature for 5 hours. Zirconium butoxide (2.5 g) is then charged andthe batch heated to 195° C. for 20 hours. The product is then cooled.

Inventive Compound 5 (IC5): Ricinoleic acid (516.6 g; 1.734 moles) andthe product of EX1 (44.7 g; 0.1176 moles) are charged to a 1 literflask, under a nitrogen sparge. The flask is attached to a Dean Starkapparatus with a stirrer. The flask is heated to 150° C. and maintainedat this temperature for 5 hours. Zirconium butoxide (2.5 g) is thencharged and the batch heated to 195° C. for 20 hours. The product isthen cooled.

Inventive Compound 6 (IC6): 12-Hydroxystearic acid (405.6 g; 1.352moles) is melted out at 100° C. in a 1 liter flask, under a nitrogensparge. The flask is attached to a Dean Stark apparatus with a stirrer.Once the 12-hydroxystearic acid, the flask is charged with melted theproduct of EX1 (89.6 g; 0.2379 moles). The flask is heated to 150° C.and maintained at this temperature for 5 hours. Zirconium butoxide (2.5g) is then charged and the batch heated to 195° C. for 20 hours. Theproduct is then cooled.

Inventive Compound 7 (IC7): 12-Hydroxystearic acid (515.6 g; 1.719moles) is melted out at 100° C. in a 1 liter flask, under a nitrogensparge. The flask is attached to a Dean Stark apparatus with a stirrer.Once the 12-hydroxystearic acid, the flask is charged with melted theproduct of EX1 (44.7 g; 0.2379 moles). The flask is heated to 150° C.and maintained at this temperature for 5 hours. Zirconium butoxide (2.5g) is then charged and the batch heated to 195° C. for 20 hours. Theproduct is then cooled.

Inventive Compound 8 (IC8): Polyisobutylenesuccinic anhydride (250.5 g;0.2386 moles) and the product of EX1 (89.6 g; 0.2357 moles) are chargedto a 1 liter flask, under a nitrogen sparge. The flask is attached to aDean Stark apparatus with a stirrer. The flask is heated to 160° C. andmaintained at this temperature for 8 hours. The flask is then heated to180° C. and held at for 5 hours. The product is then cooled.

Comparative Example 1 (CE1) is a dispersant as described in Example 2 ofGB 1 373 660.

Comparative Example 2 (CE2) is a dispersant as described in Example 5 ofU.S. Pat. No. 4,224,212.

0.38 g of each of the compounds of the invention and comparativeexamples are each dissolved in toluene (6.47 g) by warming as necessaryand added to a trident vial. 0.15 g of Solsperse®5000 (ex., The LubrizolCorporation) is added. 17 g of 3 mm diameter glass beads and 3 g ofcopper phthalocyanine pigment (Monastral Blue BG, ex Heubach) is added.The vial is capped and sealed. A control vial is also prepared that doesnot contain a dispersant. The pigment is milled by shaking on ahorizontal shaker for 16 hours. The viscosity of the resultingdispersion is assessed using an arbitrary scale of A to E (good to poor)based on stability of dispersion upon standing. The results obtained areas follows:

Compound Rating IC1 A IC2 B IC3 A IC4 A IC5 A IC6 A IC7 A IC8 B CE1 B/CCE2 C Control E

The results indicate that the compounds of the invention providesuperior fluidity of pigment dispersions in a non-polar organic medium.

Each of the documents referred to above is incorporated herein byreference. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” Unless otherwise indicated, each chemical or compositionreferred to herein should be interpreted as being a commercial gradematerial which may contain the isomers, by-products, derivatives, andother such materials which are normally understood to be present in thecommercial grade. However, the amount of each chemical component ispresented exclusive of any solvent or diluent oil, which may becustomarily present in the commercial material, unless otherwiseindicated. It is to be understood that the upper and lower amount,range, and ratio limits, set forth herein, may be independentlycombined. Similarly, the ranges and amounts for each element of theinvention may be used together with ranges or amounts for any of theother elements.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications as fall withinthe scope of the appended claims.

What is claimed is:
 1. A composition comprising a particulate solid, anon-polar organic medium, and a compound obtained by reacting anaromatic amine with a hydrocarbyl-substituted acylating agent, whereinthe aromatic amine comprises coupling products of 4-aminodiphenylaminerepresented by the formula (1a):

wherein each variable R¹ is hydrogen or a C₁₋₅ alkyl group; R² ishydrogen or a C₁₋₅ alkyl group; U is an aliphatic, alicyclic or aromaticgroup, and when U is aliphatic, the aliphatic group is a linear orbranched alkylene group containing 1 to 2 carbon atoms; and w is 0 to 9,wherein the hydrocarbyl-substituted acylating agent is an oligomer orpolymer from condensation polymerisation of a hydroxy-substituted C₁₀₋₃₀carboxylic acid into a polyester, and wherein the particulate solid is apigment or a filler.
 2. The composition of claim 1, wherein the aromaticamine to hydrocarbyl-substituted acylating agent mole ratio may be inthe range of 2:1 to 1:10.
 3. The composition of claim 1, wherein thearomatic amine to hydrocarbyl-substituted acylating agent mole ratio maybe 1:1 to 1:2.
 4. The composition of claim 1, wherein the compound isobtained/obtainable by reacting an aromatic amine with ahydroxy-substituted C₁₀₋₃₀ carboxylic acid, or mixtures thereof.
 5. Thecomposition of claim 1, wherein the hydroxy-substituted C₁₀₋₃₀carboxylic acid is polymerised to form a polyester.
 6. The compositionof claim 1, wherein the polyester has 4 to 20 repeat units of ahydroxy-substituted C₁₀₋₃₀ carboxylic acid, wherein thehydroxy-substituted C₁₀₋₃₀ carboxylic acid is a mixture of ricinoleicacid and either 12-hydroxystearic acid or 9- and 10-hydroxystearicacids.
 7. The composition of claim 1, wherein the compound is present ata range selected from 0.25 wt. % to 35 wt. % of the composition.
 8. Thecomposition of claim 1, wherein the coupling products of4-aminodiphenylamine is represented by the formula (2):


9. The composition of claim 4, wherein the hydroxy-substituted C₁₀₋₃₀carboxylic acid is ricinoleic acid, 12-hydroxystearic acid, or a mixtureof 9- and 10-hydroxystearic acids.
 10. The composition of claim 5,wherein the polyester is a polymerisation product of ahydroxy-substituted carboxylic acid of general formula HO—X—COOH,wherein X is a divalent saturated or unsaturated aliphatic radicalcontaining at least 4 carbon atoms between the hydroxyl and carboxylicacid groups.
 11. A paint or ink comprising a particulate solid, anon-polar organic medium, a film-forming resin and a compound obtainedby reacting an aromatic amine with a hydrocarbyl-substituted acylatingagent, wherein the aromatic amine comprises coupling products of4-aminodiphenylamine represented by the formula (1a):

wherein each variable R¹ is hydrogen or a C₁₋₅ alkyl group; R² ishydrogen or a C₁₋₅ alkyl group; U is an aliphatic, alicyclic or aromaticgroup, and when U is aliphatic, the aliphatic group is a linear orbranched alkylene group containing 1 to 2 carbon atoms; and w is 0,wherein the hydrocarbyl-substituted acylating agent is an oligomer orpolymer from condensation polymerisation of a hydroxy-substituted C₁₀₋₃₀carboxylic acid into a polyester; and wherein the particulate solid is apigment or a filler.
 12. The composition of claim 11, wherein the ink isan ink-jet ink, a gravure ink, or an offset ink.
 13. A compositioncomprising a compound obtained by reacting an aromatic amine with ahydrocarbyl-substituted acylating agent, wherein the aromatic aminecomprises coupling products of 4-aminodiphenylamine represented by theformula (1a):

wherein each variable R¹ is hydrogen or a C₁₋₅ alkyl group; R² ishydrogen or a C₁₋₅ alkyl group; U is an aliphatic, alicyclic or aromaticgroup, and when U is aliphatic, the aliphatic group is a linear orbranched alkylene group containing 1 to 2 carbon atoms; and w is 0,wherein the hydrocarbyl-substituted acylating agent is an oligomer orpolymer from condensation polymerisation of a hydroxy-substituted C₁₀₋₃₀carboxylic acid into a polyester, a particulate solid and a non-polarorganic medium, wherein the particulate solid is a pigment or a filler;wherein the organic medium is a plastics material and wherein theplastic material is a thermoplastic resin.